National Water-Quality Assessment Program

Transport of Anthropogenic and Natural Contaminants (TANC)

to Public-Supply Wells

An Excel® Workbook for Identifying Redox Processes in

Ground Water

Open-File Report 2009–1004

U.S. Department of the Interior

U.S. Geological Survey
An Excel® Workbook for Identifying Redox
Processes in Ground Water
By Bryant C. Jurgens, Peter B. McMahon, Francis H. Chapelle, and Sandra M.
Eberts

National Water-Quality Assessment Program

Transport of Anthropogenic and Natural Contaminants (TANC)
to Public-Supply Wells

Open-File Report 2009–1004

U.S. Department of the Interior

U.S. Geological Survey
U.S. Department of the Interior
DIRK KEMPTHORNE, Secretary

U.S. Geological Survey

Mark D. Myers, Director

U.S. Geological Survey, Reston, Virginia: 2009

For product and ordering information:

World Wide Web: http://www.usgs.gov/pubprod
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U.S. Government.

Although this report is in the public domain, permission must be secured from the individual copyright owners to
reproduce any copyrighted materials contained within this report.

Suggested reference:
Jurgens, B.C., McMahon, P.B., Chapelle, F.H., and Eberts, S.M., 2009, An Excel® workbook for identifying redox
processes in ground water: U.S. Geological Survey Open-File Report 2009–1004 8 p. Available at http://pubs.usgs.
gov/of/2009/1004/
 iii

Foreword
The U.S. Geological Survey (USGS) is committed to providing the Nation with credible scientific information that helps to
enhance and protect the overall quality of life and that facilitates effective management of water, biological, energy, and mineral
resources (http://www.usgs.gov/). Information on the Nation’s water resources is critical to ensuring long-term availability of
water that is safe for drinking and recreation and is suitable for industry, irrigation, and fish and wildlife. Population growth and
increasing demands for water make the availability of that water, now measured in terms of quantity and quality, even more
essential to the long-term sustainability of our communities and ecosystems.

The USGS implemented the National Water-Quality Assessment (NAWQA) Program in 1991 to support national, regional, State,
and local information needs and decisions related to water-quality management and policy (http://water.usgs.gov/nawqa). The
NAWQA Program is designed to answer: What is the condition of our Nation’s streams and ground water? How are conditions
changing over time? How do natural features and human activities affect the quality of streams and ground water, and where
are those effects most pronounced? By combining information on water chemistry, physical characteristics, stream habitat, and
aquatic life, the NAWQA Program aims to provide science-based insights for current and emerging water issues and priorities.
From 1991–2001, the NAWQA Program completed interdisciplinary assessments and established a baseline understanding
of water-quality conditions in 51 of the Nation’s river basins and aquifers, referred to as Study Units (http://water.usgs.gov/
nawqa/studyu.html).

Multiple national and regional assessments are ongoing in the second decade (2001–2012) of the NAWQA Program as 42 of
the 51 Study Units are reassessed. These assessments extend the findings in the Study Units by determining status and trends
at sites that have been consistently monitored for more than a decade, and filling critical gaps in characterizing the quality of
surface water and ground water. For example, increased emphasis has been placed on assessing the quality of source water
and finished water associated with many of the Nation’s largest community water systems. During the second decade, NAWQA
is addressing five national priority topics that build an understanding of how natural features and human activities affect water
quality, and establish links between sources of contaminants, the transport of those contaminants through the hydrologic system,
and the potential effects of contaminants on humans and aquatic ecosystems. Included are topics on the fate of agricultural
chemicals, effects of urbanization on stream ecosystems, bioaccumulation of mercury in stream ecosystems, effects of nutrient
enrichment on aquatic ecosystems, and transport of contaminants to public-supply wells. These topical studies are conducted in
those Study Units most affected by these issues; they comprise a set of multi-Study-Unit designs for systematic national assess-
ment. In addition, national syntheses of information on pesticides, volatile organic compounds (VOCs), nutrients, selected trace
elements, and aquatic ecology are continuing.

The USGS aims to disseminate credible, timely, and relevant science information to address practical and effective water-
resource management and strategies that protect and restore water quality. We hope this NAWQA publication will provide you
with insights and information to meet your needs, and will foster increased citizen awareness and involvement in the protection
and restoration of our Nation’s waters.

The USGS recognizes that a national assessment by a single program cannot address all water-resource issues of interest.
External coordination at all levels is critical for cost-effective management, regulation, and conservation of our Nation’s water
resources. The NAWQA Program, therefore, depends on advice and information from other agencies—Federal, State, regional,
interstate, Tribal, and local—as well as nongovernmental organizations, industry, academia, and other stakeholder groups. Your
assistance and suggestions are greatly appreciated.

Matthew C. Larsen
Associate Director for Water
iv

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 v

Contents
Abstract ...........................................................................................................................................................1
Introduction.....................................................................................................................................................1
Methods...........................................................................................................................................................2
Description of Spreadsheet Program..........................................................................................................7
Input .....................................................................................................................................................7
Redox Assignment.................................................................................................................................7
Limitations...............................................................................................................................................8
Example Dataset.............................................................................................................................................8
Acknowledgments..........................................................................................................................................8
Disclaimer........................................................................................................................................................8
References Cited............................................................................................................................................8
Redox Assignment Workbook (excel)

Figures
Figure 1. View of the worksheet used for assigning redox processes to
ground-water analyses.……………………………………………………………… 4

Tables
Table 1. Criteria and threshold concentrations used to identify redox processes
in ground water.……………………………………………………………………… 3
Table 2. Classification of redox categories and processes assigned on the basis
of water-quality data. … …………………………………………………………… 5
vi

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An Excel® Workbook for Identifying Redox Processes in
Ground Water
By Bryant C. Jurgens, Peter B. McMahon, Francis H. Chapelle, and Sandra M. Eberts
Abstract
The reduction/oxidation (redox) condition of ground
water affects the concentration, transport, and fate of many
anthropogenic and natural contaminants. The redox state of
a ground-water sample is defined by the dominant type of
reduction/oxidation reaction, or redox process, occurring in
the sample, as inferred from water-quality data. However,
because of the difficulty in defining and applying a systematic
redox framework to samples from diverse hydrogeologic
settings, many regional water-quality investigations do not
attempt to determine the predominant redox process in ground
water. Recently, McMahon and Chapelle (2008) devised
a redox framework that was applied to a large number of
samples from 15 principal aquifer systems in the United States
to examine the effect of redox processes on water quality. This
framework was expanded by Chapelle and others (in press) to
use measured sulfide data to differentiate between iron(III)-
and sulfate-reducing conditions. These investigations showed
that a systematic approach to characterize redox conditions
in ground water could be applied to datasets from diverse
hydrogeologic settings using water-quality data routinely
collected in regional water-quality investigations.
This report describes the Microsoft® Excel® workbook,
RedoxAssignment_McMahon&Chapelle.xls, that assigns the
predominant redox process to samples using the framework
created by McMahon and Chapelle (2008) and expanded by
Chapelle and others (in press). Assignment of redox conditions
is based on concentrations of dissolved oxygen (O2), nitrate
(NO3–), manganese (Mn2+), iron (Fe2+), sulfate (SO42–), and
sulfide (sum of dihydrogen sulfide [aqueous H2S], hydrogen
sulfide [HS–], and sulfide [S2–]). The logical arguments for
assigning the predominant redox process to each sample are
performed by a program written in Microsoft® Visual Basic®
for Applications (VBA). The program is called from buttons
on the main worksheet. The number of samples that can be
analyzed is only limited by the number of rows in Excel®
(65,536 for Excel® 2003 and XP®; and 1,048,576 for Excel®
2007), and is therefore appropriate for large datasets.
Introduction
The reduction/oxidation (redox) condition of ground
water affects the mobility, degradation, and solubility of
many contaminants in aquifers, including organic constituents
such as solvents and gasoline compounds and inorganic
constituents such as nitrate and arsenic. In addition, the quality
of water can be aesthetically degraded by reaction products
of redox processes, such as manganese (Mn2+), iron (Fe2+),
hydrogen sulfide gas (H2S(g)), and methane gas (CH4(g)).
For these reasons, determining redox conditions in water is
desirable for many water-quality investigations. However,
many regional ground-water-quality investigations do not
attempt to determine redox conditions in ground water because
of the difficulty in defining and applying a systematic redox
framework to samples from diverse hydrogeologic settings.
Recently, a redox framework was devised using datasets
from 15 principal aquifers in the United States (McMahon
and Chapelle, 2008). Applying the framework to other large
datasets and water-quality investigations could be aided by an
easy-to-use, automated workbook program.
The precise determination of redox conditions in
ground water is often difficult to ascertain because water
is commonly not in redox equilibrium and multiple redox
conditions may exist simultaneously as water progresses from
more oxygenated states to more reduced states. For example,
decreases in nitrate concentrations during denitrification can
occur concomitant with increases in manganese concentrations
as a result of solid-phase manganese (IV) reduction. In
addition, ground-water samples are often mixtures of water
from multiple parts of an aquifer that may have different
redox conditions. Consequently, mixing within the well bore
can produce chemistry results that suggest multiple redox
conditions. Recognizing these limitations, several researchers
have attempted to classify ground water on the basis of the
predominant redox process or the terminal electron accepting
process (TEAP) from concentrations of redox sensitive species
(Chapelle and others, 1995; Christensen and others, 2000;
Paschke and others, 2007; McMahon and Chapelle, 2008).
2   An Excel® Workbook for Identifying Redox Processes in Ground Water

Redox conditions are generally facilitated by Assignment of redox conditions is based on concentrations of
microorganisms, which gain energy by transferring electrons dissolved O2, NO3–, Mn2+, Fe2+, SO42–, and sulfide (the latter
from donors (usually organic carbon) to acceptors (usually being the sum of aqueous H2S, HS–, and S2–). The logical
inorganic species) (McMahon and Chapelle, 2008). Because arguments for assigning the predominant redox process to
some electron acceptors provide more energy than others, each sample are performed by a program written in Microsoft®
electron acceptors that yield the most energy are utilized Visual Basic® for Applications (VBA). This program is called
first and species that yield less energy are utilized in order from buttons on the main worksheet (“RedoxAssignment”
of decreasing energy gain. This process continues until all worksheet) (fig. 1).
the available donors or acceptors have been used. If carbon
sources are not a limiting factor, the predominant electron
acceptor in water will usually follow an ecological succession
from dissolved oxygen (O2), to nitrate (NO3–), to manganese Methods
(IV), to iron (III), to sulfate (SO42–), and finally to carbon
The possible outcomes of redox categories and processes
dioxide (CO2(g)) (table 1).
were differentiated by the number and type of parameters
Although some redox processes overlap as water
input into the program (table 2). Samples that had O2, NO3–,
becomes progressively more reduced, there is usually one
Mn2+, Fe2+, and SO42– were considered complete and the
TEAP that dominates the chemical signature of the water.
possible outcomes of redox categories and processes were
Consequently, the concentrations of soluble electron acceptors
determined by the logic outlined in the upper-half of table 2.
(O2, NO3–, SO42–) and TEAP end products (Mn2+, Fe2+, H2S(g),
The possible outcomes for samples that have sulfide in
CH4(g)) can be used to distinguish between redox processes.
addition to these five parameters are also included in the
Because many water-quality investigations collect O2, NO3–,
upper-half of table 2. NOTE: The actual implementation of the
Mn2+, Fe2+, and SO42–, a general framework for assessing
logic into VBA code is different than the simple “Yes,” “No”
redox processes was developed by McMahon and Chapelle
arguments in table 2. The logic used in the code was designed
(2008) using these parameters. Concentration thresholds
to execute more efficiently for a large number of samples.
were selected to apply broadly to regional ground-water-
Table 2 is a reference for users to understand the general logic
quality investigations. Although most water-quality studies
behind each redox assignment.
analyze for total dissolved manganese and iron rather than
The redox categories listed in the upper-half of table 2 are
the speciated forms of these elements, in samples that have
the same or similar to the categories listed by McMahon and
been filtered (≤0.45µm [micrometer]) and acidified, the total
Chapelle (2008). The Mixed category was further defined to
dissolved concentrations are often accurate estimates of Mn2+
indicate whether the mixture had two anoxic redox processes
and Fe2+ above the threshold concentrations (50 and 100 µg/L
[Mixed(anoxic)] or an oxic (O2-reducing) and an anoxic
[microgram per liter], respectively) used by McMahon and
redox process [Mixed(oxic-anoxic)]. The redox processes
Chapelle (2008) for pH ranges normally found in ground
comprising the mixture is separated by a “-” (meaning and).
water (6.5–8.5) (Kennedy and others, 1974; Hem, 1989).
For example, a redox process “NO3-Mn(IV)” is a mixture of
The framework of McMahon and Chapelle (2008)
nitrate- and manganese-reducing ground water. Since both
expanded on previous work (Chapelle and others, 1995;
of these redox processes are anoxic, the redox category is
Paschke and others, 2007) by including both suboxic and
“Mixed(anoxic).”
methanogenic categories. Suboxic ground water in this
Samples that have fewer than the five parameters listed
framework indicates the sample has low O2 and low NO3–, but
above were considered incomplete, and the possible outcomes
additional data is needed to further define redox processes.
of redox categories and processes are listed in the bottom-
However, McMahon and Chapelle (2008) did not differentiate
half of table 2. These samples were further differentiated
between iron (III)- and sulfate-reducing conditions because of
into two groups: (1) samples that have measured O2, but are
the lack of sulfide data in their dataset. Chapelle and others (in
missing one or more of the other four redox constituents,
press) found that iron- and sulfate-reducing conditions could
and (2) samples missing O2, but have NO3–, Mn2+, Fe2+, and
be distinguished from one another on the basis of the ratio
SO42–. Samples collected for regulatory compliance purposes
of Fe2+ to sulfide [the sum of dihydgrogen sulfide (aqueous
are often analyzed for major ions, trace elements, and
H2S), hydrogen sulfide (HS–), and sulfide (S2–) measured using
nutrients, but usually not for dissolved O2. Redox processes
colorimetric methods].
for these samples would be assigned using the logic of the
This report describes the Microsoft Excel® workbook,
second group. However, water-quality samples collected for
RedoxAssignment_McMahon&Chapelle.xls, which assigns
compliance purposes may not have been filtered or preserved
the predominant redox process to water-quality samples using
(acidified), and (or) may have been treated or blended. Users
the framework created by McMahon and Chapelle (2008)
should always evaluate the source and quality of data to
and extended by Chapelle and others (in press) (table 1).
determine if the data are suitable for redox classification.
Table 1. Criteria and threshold concentrations used to identify redox processes in ground water.
[Table was modified from McMahon and Chapelle, 2008. Redox process: O2, oxygen reduction; NO3, nitrate reduction; Mn(IV), manganese reduction; Fe(III), iron reduction; SO4, sulfate reduction; CH4gen,
methanogenesis. Chemical species: O2, dissolved oxygen; NO3-, dissolved nitrate; MnO2(s), manganese oxide with managanese in 4+ oxidation state; Fe(OH)3(s), iron hydroxide with iron in 3+ oxidation state;
FeOOH(s), iron oxyhydroxide with iron in 3+ oxidation state; SO42–, dissolved sulfate; CO2(g), carbon dioxide gas; CH4(g), methane gas. Abbreviations: mg/L, milligram per liter; —, criteria do not apply because
the species concentration is not affected by the redox process; ≤, less than or equal to; ≥, greater than or equal to; <, less than; >. greater than]
Criteria for inferring process from water-quality data
Redox Redox Nitrate,
Electron acceptor (reduction) half-reaction Dissolved
category process as Manganese Iron Sulfate Iron/sulfide
oxygen
Nitrogen (mg/L) (mg/L) (mg/L) (mass ratio)
(mg/L)
(mg/L)
Oxic O2 O2 + 4H+ + 4e– → 2H2O ≥0.5 — <0.05 <0.1 —
Suboxic Suboxic Low O2; additional data needed to define redox process <0.5 <0.5 <0.05 <0.1 —
Anoxic NO3 2NO3– + 12H+ + 10e– → N2(g) + 6 H2O; NO3- + 10H+ + 8e– → NH4+ + 3H2O <0.5 ≥0.5 <0.05 <0.1 —
Anoxic Mn(IV) MnO2(s) + 4H+ + 2e– → Mn2+ + 2H2O <0.5 <0.5 ≥0.05 <0.1 —
Anoxic Fe(III)/SO4 Fe(III) and (or) SO42– reactions as described in individual element half reactions <0.5 <0.5 — ≥0.1 ≥0.5 no data
Anoxic Fe(III) Fe(OH)3(s) + H+ + e– → Fe2+ + H2O; FeOOH(s) + 3H+ + e– → Fe2+ + 2H2O <0.5 <0.5 — ≥0.1 ≥0.5 >10
Mixed(anoxic) Fe(III)-SO4 Fe(III) and SO42– reactions as described in individual element half reactions <0.5 <0.5 — ≥0.1 ≥0.5 ≥0.3, ≤10
Anoxic SO4 SO42– + 9H+ + 8e– → HS- + 4H2O <0.5 <0.5 — ≥0.1 ≥0.5 <0.3
Anoxic CH4gen CO2(g) + 8H+ + 8e– → CH4(g) + 2H2O <0.5 <0.5 — ≥0.1 <0.5
Methods   3
4   An Excel® Workbook for Identifying Redox Processes in Ground Water
INPUT
PROGRAM
BUTTONS
Figure 1. View of the worksheet used for assigning redox processes to ground-water analyses.
Samples that have dissolved O2, but are missing one or
more of the other four constituents, will have a general redox
category of either “O2 ≥ 0.5 mg/L” or “O2 < 0.5 mg/L”. These
two categories are used to distinguish between predominately
oxic and anoxic conditions.
Samples that are missing dissolved O2, but have
measured NO3–, Mn2+, Fe2+, and SO42–, will be assigned
a redox category and process that is consistent with the
framework in table 1. However, each redox process is
amended with a prefix or suffix of “O2?” or “O2?OrNO3” to
indicate that dissolved oxygen was not measured and could
be present above the threshold concentration (table 2). The
general redox category is also amended to indicate the two
possible redox categories for O2 above or below the threshold.
The first redox category indicates the predominant redox
category that would be consistent with the other measured
data, and the second category indicates the less likely category.
For example, a sample that has low nitrate (<0.5 mg/L
OUTPUT
[milligrams per liter]) and high iron and sulfate (>100 µg/L
and >0.5 mg/L, respectively) is consistent with an Fe(III)/
SO42– reducing redox environment, so the presence of oxygen
would not be expected. Therefore, the general redox category
for this sample would be “AnoxicOrMixed(oxic-anoxic)”
to indicate this sample is most likely anoxic but would be
a mixed sample if dissolved O2 was greater than 0.5 mg/L.
Conversely, a sample containing high NO3– and low Mn2+
and Fe2+ is consistent with both an O2– and a NO3—reducing
environment, as indicated by the “O2?OrNO3” designation in
table 2. McMahon and Chapelle (2008, table 2) showed that
most ground-water samples (greater than 50 percent) tend
to be O2 reducing while only a small percentage (less than
4 percent) tend to be NO3– reducing for many hydrogeologic
settings. Consequently, these samples are assigned a general
redox category of “OxicOrAnoxic” to indicate that the oxic
condition is more likely than the anoxic condition, although
this assumption may not be valid in some settings.
Table 2. Classification of redox categories and processes assigned on the basis of water-quality data.
Table 2. Classification of redox categories and processes assigned on the basis of water-quality data.—Continued
[Redox category: O2 ≥ 0.5 mg/L, dissolved oxygen greater than or equal to 0.5 mg/L; O2 < 0.5 mg/L, dissolved oxygen less than 0.5 mg/L. Redox process: O2, oxygen reduction; NO3, nitrate reduction;
[Redox category: O2 ≥ 0.5 mg/L, dissolved oxygen greater than or equal to 0.5 mg/L; O2 < 0.5 mg/L, dissolved oxygen less than 0.5 mg/L. Redox process: O2, oxygen reduction; NO3, nitrate reduction;
Mn(IV), manganese reduction; Fe(III), iron reduction; SO4, sulfate reduction; CH4gen, methanogenesis. Abbreviations: mg/L, milligram per liter; <, less than; ≤, less than or equal to; ≥, greater than or equal
Mn(IV), manganese reduction; Fe(III), iron reduction; SO4, sulfate reduction; CH4gen, methanogenesis. Abbreviations: mg/L, milligram per liter; <, less than; ≤, less than or equal to; ≥, greater than or
to; >, greater than; Y, yes; N, no; —, criteria do not apply because the species concentration is not affected by the redox process; ?, insufficient data to determine whether process is occuring or not; /, and (or);
equal to; >, greater than; Y, yes; N, no; —, criteria do not apply because the species concentration is not affected by the redox process; ?, insufficient data to determine whether process is occuring or not; /,
-, and; x, not applicable]
and (or); -, and; x, not applicable]
Dissolved Nitrate, Iron/sulfide Iron/sulfide
Redox Redox Manganese Iron Sulfate
oxygen as Nitrogen mass ratio mass ratio
Category Process >0.05 mg/L >0.01 mg/L >0.5 mg/L
>0.5 mg/L >0.5 mg/L >0.3 >10
Water-quality data complete
Oxic O2 Y — N N — x x
Suboxic Suboxic N N N N — x x
Anoxic NO3 N Y N N — x x
Anoxic Mn(IV) N N Y N — x x
Anoxic Fe(III)/SO4 N N — Y Y no data no data
Anoxic CH4gen N N — Y N x x
Mixed(oxic-anoxic) O2-Mn(IV) Y — Y N — x x
Mixed(oxic-anoxic) O2-Fe(III)/SO4 Y N — Y Y no data no data
Mixed(oxic-anoxic) O2-CH4gen Y N — Y N x x
Mixed(anoxic) NO3-Mn(IV) N Y Y N — x x
Mixed(anoxic) NO3-Fe(III)/SO4 N Y — Y Y no data no data
Mixed(anoxic) NO3-CH4gen N Y — Y N x x
Anoxic SO4 N N — Y Y N N
Mixed(anoxic) Fe(III)-SO4 N N — Y Y Y N
Anoxic Fe(III) N N — Y Y Y Y
Mixed(oxic-anoxic) O2-SO4 Y N — Y Y N N
Mixed(oxic-anoxic) O2-Fe(III)-SO4 Y N — Y Y Y N
Mixed(oxic-anoxic) O2-Fe(III) Y N — Y Y Y Y
Mixed(anoxic) NO3-SO4 N Y — Y Y N N
Mixed(anoxic) NO3-Fe(III)-SO4 N Y — Y Y Y N
Mixed(anoxic) NO3-Fe(III) N Y — Y Y Y Y
Methods   5
Table 2. Classification of redox categories and processes assigned on the basis of water-quality data.—Continued
[Redox category: O2 ≥ 0.5 mg/L, dissolved oxygen greater than or equal to 0.5 mg/L; O2 < 0.5 mg/L, dissolved oxygen less than 0.5 mg/L. Redox process: O2, oxygen reduction; NO3, nitrate reduction;
Mn(IV), manganese reduction; Fe(III), iron reduction; SO4, sulfate reduction; CH4gen, methanogenesis. Abbreviations: mg/L, milligram per liter; <, less than; ≤, less than or equal to; ≥, greater than or
equal to; >, greater than; Y, yes; N, no; —, criteria do not apply because the species concentration is not affected by the redox process; ?, insufficient data to determine whether process is occuring or not; /,
and (or); -, and; x, not applicable]
Dissolved Nitrate, Iron/sulfide Iron/sulfide
Redox Redox Manganese Iron Sulfate
oxygen as Nitrogen mass ratio mass ratio
Category Process >0.05 mg/L >0.01 mg/L >0.5 mg/L
>0.5 mg/L >0.5 mg/L >0.3 >10

Water-quality data incomplete

O2 ≥ 0.5 mg/L Unknown Y no data no data no data no data no data no data
O2 < 0.5 mg/L Unknown N no data no data no data no data no data no data
OxicOrAnoxic O2?OrNO3 no data Y N N Y x x
OxicOrSuboxic O2?OrSuboxic no data N N N N x x
AnoxicOrMixed(oxic-anoxic) Mn(IV)-O2? no data N Y N — x x
AnoxicOrMixed(oxic-anoxic) Fe(III)/SO4-O2? no data N — Y Y no data no data
AnoxicOrMixed(oxic-anoxic) CH4gen-O2? no data N — Y N x x
Mixed(anoxic)Or(oxic-anoxic) Mn(IV)- no data Y Y N — x x
O2?OrNO3
Mixed(anoxic)Or(oxic-anoxic) Fe(III)/SO4- no data Y — Y Y no data no data
O2?OrNO3
Mixed(anoxic)Or(oxic-anoxic) CH4gen- no data Y — Y N x x
O2?OrNO3
AnoxicOrMixed(oxic-anoxic) SO4-O2? no data N Y Y Y N N
Mixed(anoxic) Fe(III)-SO4-O2? no data N Y Y Y Y N
6   An Excel® Workbook for Identifying Redox Processes in Ground Water

AnoxicOrMixed(oxic-anoxic) Fe(III)-O2? no data N Y Y Y Y Y

Indeterminate Unknown no data no data no data no data no data no data no data
 Description of Spreadsheet Program   7

followed by a number—for example, “<0.2,” “E10.5,” or

Description of Spreadsheet Program “>50.” In general, the first mixed character-number format
indicates the value is less than the laboratory reporting limit,
The Microsoft® Excel® workbook, RedoxAssignment_
the second an estimated value, and the third a value greater
McMahon&Chapelle.xls, consists of two worksheets and
than the analytical limit. Once the program identifies a mixed
a VBA program that determines the predominant redox
character-number formatted value, the text character, either
process in each sample according to table 2. The first
the “<”, “E”, or “>”, will be removed and the number retained
worksheet, named “Instructions,” provides brief instructions
before the program assigns a redox state.
on the use of the program. The second worksheet, named
All constituents used for determining redox processes
“Redox Assignment,” is the main worksheet where data are
should be analyzed with method reporting levels equal to or,
entered and redox processes and categories are assigned.
preferably, lower than the threshold concentrations listed in
The workbook includes a set of 32 example analyses, each
tables 1 and 2. The use of analyses with higher reporting levels
representing one of the unique redox assignments listed in
will likely result in incorrect redox classifications.
table 2. NOTE: Because this workbook contains a VBA
Total manganese and total iron concentrations above the
program, the program will not operate unless macros are
threshold concentrations (50 and 100 µg/L) from samples
enabled in Microsoft® Excel®.
that have been filtered (≤0.45 µm) and acidified and are
The Sample ID, and concentrations of dissolved
often accurate measurements of dissolved Mn2+ and Fe2+
O2, NO3–, Mn2+, Fe2+, and SO42– are required for a redox
at pH ranges normally measured in ground water (6.5–8.5)
assignment using the classification scheme by McMahon
(Kennedy and others, 1974; Hem, 1989). Consequently, it
and Chapelle (2008). Samples that have measured sulfide
may be acceptable to use total dissolved concentrations of
concentrations will be further defined to distinguish iron(III)-
manganese and iron as substitutes for Mn2+ and Fe2+. Other
reducing from sulfate-reducing conditions, as described by
data may be equally acceptable; however, all water-quality
Chapelle and others (in press). Samples having only dissolved
data should be evaluated to determine if the data are suitable
O2, or are missing one or more of the other redox species, will
for redox classification.
be classified as either “O2 ≥ 0.5 mg/L” or “O2 < 0.5 mg/L.”
A redox process will also be assigned to samples lacking O­­2
data but having NO3–, Mn2+, Fe2+, and SO42– data. The redox Redox Assignment
process determined for these samples is consistent with the
framework created by McMahon and Chapelle (2008), but , The program is operated by two buttons located in the
as noted above, is amended with an “O2?” or “O2?OrNO3” second column on the left-hand side of the main worksheet
to include the possibility that dissolved oxygen could be (figure 1). These two buttons control the contents of the cells
present at concentrations above the threshold. Without O2 data, in columns I thru L. The number of samples to be analyzed is
oxygen-reducing and nitrate-reducing ground water cannot be determined by the number of non-null cells in column A, so a
distinguished. Sample ID must be assigned to every sample before running
the program. The number of samples that can be analyzed
is only limited by the number of rows in Excel® (65,536 for
Input Excel® 2003 and XP and 1,048,576 for Excel® 2007). The
“Clear Redox Assignments” button clears the contents of
Data can be copied from other spreadsheets or programs
cells in columns I thru L. The “Assign Redox Categories and
into the corresponding constituent columns on the main
Processes” button assigns a redox process and category to
spreadsheet (“RedoxAssignment” worksheet, fig. 1).
each sample according to the logic in table 2.
The program accepts constituent concentrations in either
Column I is a count of the number of constituents.
milligrams per liter (mg/L) or micrograms per liter (µg/L).
Column J is the general redox category defined in table 2, and
The concentration units can be changed using the pull down
column K is the redox process defined in table 2. Column L is
menu in row 2 below each constituent and must be defined
the calculated Fe2+ to sulfide ratio for samples having sulfide
before running the program to ensure the use of accurate
in addition to the five required parameters. Mixed samples
thresholds and ratios of Fe2+ to sulfide. Input concentrations
are identified in the General Redox Category column and a
should be formatted as a number and preferably should not
hyphen, “-,“ is added to separate the two redox processes of
contain text characters. The program will accept 3 types of
the mixture in the Redox Process column.
mixed character-number formats. The first character must
be either a “<,” “E” (case sensitive), or “>,” and must be
8   An Excel® Workbook for Identifying Redox Processes in Ground Water
Limitations
The redox framework described by McMahon and
Chapelle (2008) has some limitations and inherent uncertainty.
These limitations are described more fully by McMahon and
Chapelle (2008) and Chapelle and others (in press). In general,
most of the uncertainty is derived from defining appropriate
thresholds that accurately identify the predominant terminal
electron acceptor process for many water analyses with
varied chemistry from diverse hydrogeologic settings. The
thresholds used here were defined to be broadly applicable
to large datasets for regional studies across different
hydrogeologic settings. Threshold concentrations and the
relative importance of each redox process could be further
refined using site-specific information. To change threshold
concentrations, users can change the threshold values listed
in row 3 on the main worksheet (“RedoxAssignment”
worksheet, fig. 1). NOTE: The cells containing the original
threshold concentrations in row 3 contain a formula that will
be lost after manually changing the values in these cells.
It is suggested that the user save any altered version of the
workbook separately from the original workbook.
Example Dataset
The workbook includes a sample dataset
(“RedoxAssignment” worksheet, fig. 1) that is a subset of
samples from wells used in the report by McMahon and
Chapelle (2008). Each sample well has a chemistry analysis
representing one of the redox categories and the corresponding
redox process given in table 1. Some of the samples were
duplicated to illustrate how sulfide concentrations may affect
the redox assignment, using the criteria described by Chapelle
and others (in press). The sulfide concentrations from
these samples are not actual measured data. Other samples
were duplicated, and dissolved O2 data was removed to
demonstrate the redox process assignments and general redox
categories for samples lacking O2 data. The redox process
assignments for these samples were amended with an “O2?”
or “O2?OrNO3.”
Acknowledgments
The funding for this report and development of this
program was provided by the U.S. Geological Survey’s
National Water-Quality Assessment (NAWQA) program’s
“Transport of Anthropogenic and Natural Contaminants
(TANC) to supply wells” topical team.
Disclaimer
This program contains Microsoft® Visual Basic® code
that was written to determine the predominant redox process
in ground-water samples based on the work of McMahon
and Chapelle (2008) and Chapelle and others (in press).
All efforts have been made to ensure the program makes
accurate determinations; however, it is possible that errors
within the code may exist or that certain formats of input data
could cause a redox process to be assigned in error or not
at all. Users are encouraged to keep an original copy of the
workbook and notify the author if any errors are found.
Author Contact Information
Bryant Jurgens, Hydrologist
(916) 278-3275, bjurgens@usgs.gov
References Cited
Chapelle, F.H., McMahon, P.B., Dubrovsky, N.M., Fujii,
R.F., Oaksford, E.T., and Vroblesky, D.A., 1995, Deducing
the distribution of terminal electron-accepting processes
in hydrologically diverse groundwater systems: Water
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Chapelle, F.H., Bradley, P.M., Thomas, M.A., and McMahon,
P.B., in press, Distinguishing iron-reducing from sulfate-
reducing conditions in ground-water systems: Ground
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